Stabilization of crops



Paten'tecl Aug. 17, 1954 STABILIZATION OF CROPS Joseph A. Chenicek, Bensenville, 111., assignor to Universal Oil Products Company, Chicago, 111., a corporation of Delaware No Drawing. Application July 28, 1950, Serial No. 176,531

9 Claims.

This invention relates to the stabilization of crops and more particularly to a novel method of preserving the desirable qualities thereof.

Drying of crops in the field or in drying equipment results in a loss of valuable food accessory factors. The present invention is directed to the use of a novel inhibitor for preventing this loss. An important requirement of a satisfactory inhibitor is that it is substantially non-volatile under the conditions of use so that it will not be evaporated and lost during the drying treatment. The novel inhibitors of the present invention will be retained during the drying treatment and thereby will serve to stabilize the crops.

The term crops as used in the present in vention is intended to include any substance grown from the soil to be used as a food for humans or animals, either in the form as gathered from the field or after suitable modification in form, such as by pressing, grinding, pulverizing, slurrying, making into paste, flour, etc., either used as such or after suitable cooking. Thus the present invention is applicable to the treatment of forage crops, such as alfalfa, clover, hay, fodder, etc.; grains such as corn, wheat, oats, rice, barley, rye, soy beans, etc.; vegetables such as carrots, peas, spinach, beets, potatoes, parsley, cabbage, etc.; fruits including both small fruits and those grown on trees, such as berries, oranges, lemons, grapefruit, apples, bananas, melons, dates, figs, etc. nut crops including peanuts, walnuts, pecans, almonds, chestnuts, hazel nuts, etc.; hops, coffee, tea, sugar, etc. Also included are crops such as tobacco, which although not actually consumed as such, are chewed and the oils therefrom are allowed to enter into the system. It is understood that the above crops are merely typical representatives and that the broad scope of the present invention is not intended to be unduly limited to the crops specifically mentioned but is to include all other crops subject to oxidative deterioration.

During the drying treatment alfalfa loses anywhere from 45% to 85% of its carotene value. Similarly, carotene is found in sweet potatoes and in other yellow pigmented plants. Vitamin B1 (thiamine hydrochloride) is found in various seeds, grains, nuts, legumes, fruits and vegetables, while vitamin B2 (riboflavin) is found in wheat germ andleafy vegetables. Nicotinic acid (Niacin) is found in wheat germ and in several green leafy vegetables, while vitamin B6 (pyridoxine) is found in whole grain cereals, crude cane molasses, etc. Vitamin C (ascorbic acid) is found in citrus fruits, tomatoes, green peppers and various other fresh fruits and vegetables, and vitamin E is found in wheat germ oil, cottonseed oil, green leafy vegetables and various grains. Vitamin K1 is found in alfalfa, spinach, and other green vegetables. Pantothenic acid is found in crude cane molasses and Wheat germ. Several postulated vitamins which have not as yet been completely accepted, such as citrin, gizzard erosion factor, etc., are found in various crops, the citrin being present in citrus foods, and the gizzard erosion factor being present in alfalfa, kale, etc. It is understood that the above is merely a brief reference to the vitamin content of various crops and that these and other crops may also contain other vitamins as, for example, spinach contains vitamins A, B2 later known as vitamin G (riboflavin) and C, beets contain vitamin B1, potatoes contain vitamin B2, parsley, cabbage, and berries contain vitamin C, etc.

In addition to vitamins or in absence of vitamins, various crops contain other desirable substances which tend to deteriorate due to oxidative deterioration. For example, various fatty acids, such as caprylic, capric, lauric, myristic, palmitic, stearic, oleic, linoleic, etc., are found in the oils of coconut, babassu, palm kernel, olive, castor, peanut, rapeseed, cottonseed, corn, soy bean, etc. Alcohols are found in cockfoot grass, wheat, lucerne leaf, etc. Various sterols are found in plant oils, ergosterol, for example, being found in soya bean oil. Further, crops may become rancid and lose desirable qualities such as taste, odor, retention of physical shape (nonwilting), etc, due to oxidative deterioration.

In one embodiment the present invention relates to a process for stabilizing crops subject to oxidative deterioration which comprises apply-- ing thereto a l\T,N-di-alkylene-p-phenylene diamine wherein the alkylene groups contain from a to 12 carbon atoms each.

In a specific embodiment the present invention relates to a process for stabilizing carotene con taining crops subject to oxidative deterioration which comprises spraying said crops with an inhibitor comprising a N,N-di-alky1ene-p-phenylene diamine, each of the alkylene groups containing from 6 to 8 carbon atoms.

In a more specific embodiment the present invention relates to a process for stabilizing alfalfa which comprises spraying alfalfa with an inhibitor comprising N,N-di-hexylene-p-ph'enylene diamine.

It is an essential feature of the present; invention that each of the alkylene groups substituted on the nitrogen atoms of the p-phenylene diamine contains from 6 to 12 carbon atoms and preferably from 6 to 8 carbon atoms. As hereinbefore set forth, the inhibitors of the present invention are substantially non-volatile under the conditions of use and thereby will not be evaporated during the drying treatment. Further, the alkylene groups should conatin not more than 12 carbon atoms per molecule because longer chain alkylene groups decrease the potency of the inhibitor compound and, therefore, will prove unsatisfactory for the purpose intended.

Another advantage of the inhibitors of the present invention is that they are not water soluble and, when applied in the field, will not be washed away by rain or, when applied after cutting will not be removed during subsequent washing oi the crops. Another advantage to inhibitors of the present invention is that they are wax soluble and, therefore, will penetrate through the waxy coating of various crops and will enter into the cells of the crops to effect stabilization of the oil therein.

Representative examples of inhibitors of the invention are N,N-di-heXylene-p-phenylene diamine, N,N-di-heptylene-p-phenylene diamine, N,N -di-octylene-p-phenylene diamine, N,N -dinonylene-p-phenylene diarnine, N,N-di-decylene-p-phenylene diamine, N,N-di-undecylene-pphenylene diamine and N,Ndi-dodecylene-p phenylene diamine.

It is understood that the allzylene groups may be straight or branched chain. The branched chain groups may contain one or more branching in the chain. The inhibitor compounds may be prepared by the reductive alkylation of p-phenylene diamine or p-nitroaniline with mesityl oxide, vinyl butyl ketone, phorone, etc. It is understood that these compounds may be prepared by the reductive alkylation of p-phenylene diarnine or p-nitroaniline with a suitable ketone or aldehyde. A particularly preferred catalyst for efieoting the reaction comprises a mixture of the oxides of chromium, copper and barium, although other suitable catalysts may be employed. In general, the reaction is effected at an elevated temperature of from about 100 to about 250 C. and a hydrogen pressure of from about to about 200 atmospheres.

It is understood that the various inhibitors which may be prepared and used within the broad scope of the present invention are not necessarily equivalent in their activity but they all will serve to stabilize the crops to some degree.

The inhibitor may be applied to the crops in any suitable manner and either before or after cutting. In a preferred embodiment of the invention, the inhibitor is sprayed or dusted on the crops. When the inhibitor is liquid, it may be sprayed as such and, where the inhibitor is a solid, it may be dusted on the crops or dissolved in a suitable non-toxic organic solvent or emulsified with a wetting agent and then sprayed on the crops. A particularly suitable solvent comprises vegetable oils such as corn oil, soy bean oil, sesame oil, peanut oil, etc. or it may comprise a light hydrocarbon naphtha or'kerosene which is volatile and will evaporate to leave the inhibitor absorbed in the crops. In some cases the solvent may comprise an alcohol, ether, aldehyde, ketone, etc. When utilized as an emulsion the inhibitor may be commingled with a wetting agent, such as Aerosol, Nacconol, Santomerse, etc. or those of the gardinol type and, in fact, with any suitable non-toxic wetting agent. In still another embodiment, the liquid inhibitor may be emulsified with water and then used as a spray or made in a solution with the various solvents hereinbefore set forth and then emulsified with the wetting agent, with or without a solutizing agent, and utilized as such or in a solution or emulsion with water. For dusting, the inhibitor or a solution or emulsion thereof as hereinbefore set forth may be admixed with suitable inert material, such as clays.

The inhibitor may be sprayed or dusted by hand or from aeroplanes or by any other suitable method in order to distribute the inhibitor in finely divided particles over the crops, either as droplets or as finely divided solid particles. The inhibitor will penetrate throughout and within the leaves, seeds, etc., of the crops and will thereby serve to preserve the desirable qualities, not only of the leaves themselves, but also of the oils and the like obtained from the crops. Similarly, the inhibitor will penetrate into the larger produce such as oranges, lemons, melons, apples, pears, etc. and thereby will serve to preserve the vitamin content and other. desirable properties thereof.

The inhibitors may be sprayed or dusted alone or in combination with insect or weed killing materials. In some cases, the insect or weed killing material may serve as a solvent for the inhibitor as, for example, when it is desired to use a hydrocarbon fraction, such as kerosene, for this purpose.

t is understood that the spraying or dusting of the crops may be done while the crops are in the field, either prior to or after cutting, or that the inhibitor may be applied after the crops have been gathered and stored. The amount of in hibitor to be applied to the crops may vary considerably, but in general will range from about 0.0001% to 0.5% or more by weight of active ingredient.

The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.

Example I Alfalfa containing 28 mg. of carotene per grams will lose approximately 50% of its carotene content when stored at 75 F. for 7 weeks. However, upon the addition of N,N'-di-hexylene-pphenylene diamine dissolved in soya bean oil, in an amount of 0.25% by weight based on active inhibitor compound, the alfalfa will lose only approximately '7.5% of its carotene value at the end of 7 weeks when stored at 75 F.

Example II When the alfalfa is stored at F. for 7 weeks, 'it will lose approximately 77% of its carotene content. However, upon the addition of 0.25% by weight of the active inhibitor compound described in Example I, the alfalfa will lose only about 24% or" its carotene content.

I claim as my invention:

1. A process for stabilizing crops subject to oxidative deterioration which comprises applying thereto an inhibitor comprising a N,l\l-di-allylene-p-phenylene diamine wherein the alkylene groups contain from 6 to 12 carbon atoms each.

2. A process for stabilizing carotene containing crops subject to oxidative deterioration which comprises applying thereto an inhibitor comprising N,N"-di-alkylene-p-phenylene diamine wherein the alkylene groups contain from 6 to 8 carbon atoms each.

3. A process for stabilizing carotene containing crops subject to oxidative deterioration which comprises distributing over the crops finely divided particles of an inhibitor comprising N,N- di-alkylene-p-phenylene diamine wherein the alkylene groups contain from 6 to 8 carbon atoms each.

4. A process for stabilizing alfalfa to prevent loss in carotene content which comprises spraying the alfalfa with an inhibitor comprising a N,N'-di-hexylene-p-phenylene diamine.

5. A process for stabilizing alfalfa to prevent loss in carotene contentwhich comprises spraying the alfalfa with an inhibitor comprising a N,N-di-octylene-p-phenylene diamine.

6. Crops normally subject to oxidative deterioration and containing as an inhibitor against said deterioration a N,N'-di-alkylene -pphenylene diamine wherein the alkylene groups contain from 6 to 12 carbon atoms each.

7. Crops having a carotene content normally 6 subject to oxidative deterioration and containing, as an inhibitor against said deterioration, a N ,N- di-alkylene-p-phenylene diamine wherein the alkylene groups contain from 6 to 8 carbon atoms each.

8. Alfalfa containing a N,N-di-hexylene-pphenylene diamine as an inhibitor against loss in carotene content.

9. Alfalfa containing a N,N-di-octylene-pphenylene diamine as an inhibitor against loss in carotene content.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,474,182 Kephart June 21, 1949 2,498,630 Thompson Feb. 28, 1950 2,513,002 Chenicek June 27, 1950 

1. A PROCESS FOR STABILIZING CROPS SUBJECT TO OXIDATIVE DETERIORATION WHICH COMPRISES APPLYING THERETO AN INHIBITOR COMPRISES A N,N''-DI-ALKYLENE-P-PHENYLENE DIAMINE WHEREIN THE ALKYLENE GROUPS CONTAIN FROM 6 TO 12 CARBON ATOMS EACH. 